Effect of truncating electrostatic interactions on predicting thermodynamic properties of water–methanol systems
A. Rahbari (TU Delft - Engineering Thermodynamics)
R. Hens (TU Delft - Engineering Thermodynamics)
Seyed Hossein Jamali (TU Delft - Engineering Thermodynamics)
M. Ramdin (TU Delft - Engineering Thermodynamics)
David Dubbeldam (Universiteit van Amsterdam, TU Delft - Engineering Thermodynamics)
Thijs J.H. Vlugt (TU Delft - Engineering Thermodynamics)
More Info
expand_more
Other than for strictly personal use, it is not permitted to download, forward or distribute the text or part of it, without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license such as Creative Commons.
Abstract
The combination of the TraPPE and OPLS/2016 force fields with five water models, TIP3P, SPC/E, OPC, TIP4P/2005 and TIP4P/EW was used to compute mixing enthalpies, excess chemical potentials and activity coefficients of water and methanol. Excess chemical potentials and activity coefficients were computed in an expanded version of the NPT ensemble. We found the best agreement between experimental data for all the computed properties of water–methanol mixtures for the TIP4P/2005-TraPPE force fields. The performance of the spherical cutoff methods in MC and MD simulations was compared to the Ewald summation. The radial distribution functions obtained from the Ewald summation and the Damped-Shifted Force (DSF) method were in excellent agreement. Numerical artifacts appeared at the cutoff radius when the original Wolf method was used to calculate the electrostatic interactions. The calculated excess mixing enthalpies, excess chemical potentials, and activity coefficients of water and methanol obtained from the Wolf method were in good agreement with the DSF method. Our simulation results show that the numerical artifacts of the original Wolf method have little effect for energy calculations in aqueous methanol mixtures.
help_outline